Novel reading inhibit agents

ABSTRACT

Disclosed is an optical disk, card or media which comprises: a) a plurality of data structures that are readable by the interrogating beam of light; and b)a composition on or in the optical disk, card or media disposed so that when the optical disk, card or media is used in the optical read-out system, the interrogating beam of light passes through the composition before or after contacting some or all of the data structures. The composition comprises a polymeric matrix with an organometallic complex dissolved therein or with metal, transition metal, metal oxide or transition metal oxide nanoparticles uniformly dispersed therein. The composition is substantially transparent to the interrogating beam and/or is substantially colorless. Alternatively, the composition comprises a solid polymeric matrix with an olefinic compound dissolved or uniformly dispersed therein wherein double bond in the olefinic compound undergoes oxidative cleavage promoted by a transition metal catalyst and a thiophenol or a catalytic amount of a thiyl radical and wherein the composition is substantially transparent to the interrogating beam and/or is substantially colorless.

RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. ProvisionalApplication Serial No. 60/332,889, filed Nov. 6, 2001, the entireteachings of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

[0002] This invention relates to a method of using materials that areapplied to a disk or card or the like, such as would be used for storinginformation, such that upon subsequent exposure to an ambient conditionsaid applied material changes from a substantially transparent state toone that is substantially more opaque as a consequence of the creationof light scattering centers, color change, and/or reflectivity change,thereby limiting the ability to read information from said disk, card,or the like after the desired information has been read from the diskfor a certain duration of time.

[0003] U.S. Pat. No. 5,815,484 describes a limited play optical diskusing photochromism, defined as a phenomenon whereby irradiation of amaterial by light exhibiting desirable wavelengths effects reversible orirreversible changes to the optical absorbance of the material. Inparticular, irradiation of a coating comprising a photochromic materialby light alters the reactive material in the coating so as to change thecoating from an optically transparent to an optically opaque state. Morespecifically, the aforementioned prior art describes the combination oflight and oxygen as the stimulus that changes the absorbancecharacteristics of a photochromic material in response to aninterrogating beam of light having a wavelength desirably of about 650nm. It further describes that when the stimulus is exclusively air, suchas from the ambient environment, then the reactive material, which forexample comprises a compound selected from a group of dye molecules,changes its state as a result of oxidation from an optically transparentto an optically opaque state that absorbs light of desirable wavelengthsused for reading the information from the disk. The active material isdescribed as preferably superimposed over some or all of the pluralityof data structures in the optical disk, in the form of a coating on aleast a portion of the outer surface of the substrate. U.S. Pat. No.5,815,484 further specifies that if the material were to be interposedbetween the substrate and the metallic layer then it would be inherentlymore difficult to manufacture the optical disk.

[0004] Compounds I and II, of U.S. Pat. No. 5,815,484, specificallyreact upon exposure to 650 nm light at an intensity consistent with thelight sources for current DVD players. Moreover, these compounds arephotoreactive in the presence of oxygen from ambient air upon exposureto either incandescent or fluorescent light. Accordingly, it is requiredthat compounds I and II, as part of a coating applied to a disk, bestored in inert environment, free of oxygen, prior to exposure to thelight from sources such as semi-conductor lasers used for the DVDplayers. U.S. Pat. No. 5,815,484 also specifies that oxygen reactivematerials, for example, the dye compound methylene blue, can be used asthe reactive compound that in its reduced form exhibits a pale yellowcolor, and which re-oxidizes to a dark blue color upon exposure tooxygen in ambient air. This dye and other described dye materials onlyrequire exposure to oxygen, and not to the combination of oxygen andlight, for the desired change in absorbance characteristics.Accordingly, it is also necessary to store the optical disk containing acoating comprising such dyes in an inert environment free of oxygenprior to use in a CD or DVD player. This requires special packaging toprevent or substantially limit diffusion of oxygen, and perhaps also theuse of oxygen adsorbing compounds as part of the packaging. Moreover,once the special packaging is removed and the disk is exposed to ambientconditions, then the coating applied to the disk and which contains thereactive materials must also have been protected against solvents thatcould subsequently be used to remove or alter said reactive materials,and also protected from use of mechanical methods, such as, for example,polishing or grinding that could be used to remove said coating. The useof such reactive compounds does not contemplate the future use ofsemi-conductor lasers with shorter wavelengths for more advanced opticaldisk technologies. Specifically, the dye compounds described would notbe appropriate for DVD players incorporating the use of lasers emittingat say 405 nm.

[0005] U.S. Pat. No. 5,815,484 claims a method of limiting access todata stored on an optical medium wherein said disk comprises an areacontaining a plurality of readable data structures and which iscoincident with a reactive compound superimposed over at least a portionof said data structures of said area. The reactive compound is to beoperated in an ambient environment containing oxygen and the absorbanceof light by the material, in response to a combination of exposure tooxygen and to irradiation for some duration of time by light having awavelength within a selected range, is altered causing a change inoptical transmission from said area. A requirement of exposure to bothambient environment and irradiation for some duration of time isparticularly disadvantageous. The intensity of semiconductors lasersused in CD and DVD players is not uniform from different manufacturersand thus the duration of time for said irradiation will vary fordifferent players. Moreover, the selected range of wavelengths for saidirradiation would be difficult to implement, using the methodscontemplated, for a range as broad as between about 780 nm and 405 mn,as would be necessary to prevent defeatability of limited play atshorter wavelengths and provide for useful backwards compatibility.

[0006] U.S. Pat. No. 5,815,484 further claims an optical disk adaptedfor use in an optical readout system such that the disk comprises a filmof a reactive compound which is operative to change in response to astimulus applied to the reactive compound. The film is disposed as anoverlayer on a substrate that is in a confronting relationship with areflecting metallic layer or interposed between said metallic layer andthe substrate. Said stimulus is either visible light, infrared light, anambient environment containing light and oxygen, or air. When theclaimed optical disk is adapted specifically for the stimulus being onlyair, then the reactive compound is operative after a duration of timeneeded to oxidize and change the absorbance characteristics of thematerial between a transparent and suitably opaque state that absorbslight of the desired wavelength. An optical disk containing a filmcomprising said reactive compound that is a chemically reduced form of adye is further claimed. It is also further claimed that an improvedoptical disk contains a reactive compound responsive to irradiation bythe interrogating beam such that the chemical characteristic of thecompound is intentionally changed between transparent and suitablyopaque states by exposure to the light, such that the altered reactivecompound absorbs light of desired wavelengths. The intensity ofsemiconductors lasers used in CD and DVD players is not uniform fromdifferent manufacturers and thus the required reduction in absorbance ofthe desired wavelengths will vary for different players. Additionally,the signal to noise requirements for detection of reflected light forreading from DVD and CD media by photo-detectors in said players is notuniform for players from different manufacturers. Moreover, absorbanceof the selected range of wavelengths would be difficult to implement,using the methods contemplated, for a range as broad as between about780 nm and 405 nm, as would be necessary to prevent defeatability oflimited play at other wavelengths and provide for useful backwardscompatibility U.S. Pat. No. 5,815,484 additionally claims a method forlimiting access to data stored on an optical disk having a substrate, ametallic layer encoded with information, and a reactive layer throughwhich the radiation passes prior to being reflected for reading, whereinthe reactive layer is exposed to an unspecified environmental stimulusthat changes the optical characteristic of said reactive layer from anoptically transparent state to an optically opaque state. The claimedmethod suffers from a serious disadvantage that in practice cansubstantially compromise and defeat the intended objective. Although thepatent specifies the importance of a method for forming an opaque statein the reactive layer that absorbs light of the desired wavelengths,opacity is not defined as being able to withstand defeatability of thedesired absorbance state that may otherwise occur due to subsequentexposure of the disk to light containing UV and/or visible wavelengths.Exposure of a disk comprising the reactive material to light, such asreadily available and obtained from sunlight, mercury arc lamps, Xenonflash lamps, etc. will generally photobleach the opacity of a reactivelayer comprising reactive compounds that are photoactive materials suchas defined in U.S. Pat. No. 5,815,484. Photobleaching herein is definedas causing a substantial decrease of said opacity exhibited by thereactive layer. Complete photobleaching of the photoactive material inthe reactive layer causes said layer to exhibit a change from saidopacity to a state of relative transparency. Specifically, U.S. Pat. No.5,815,484 contemplates and claims the use of quasi-stable photochromiccompounds, such as spiropyrans, and the use of organic dye moleculessuch as methylene blue and related compounds. U.S. Pat. No. 5,815,484did not contemplate that the preferably formed state of opacity in thereactive layer comprising said photoactive compounds can bephotobleached, especially when said compounds are present in anenvironment that can alter the oxidized state, and consequently thedesired absorbance state at certain wavelengths can be modified to causethe reactive layer to exhibit a relatively undesired transparent state.Similarly, undesirable photobleaching can effect a diminution in thelevel of absorbance exhibited at the desired wavelengths, as well as ashift in the absorbance spectrum such that absorbance at the desiredwavelengths diminishes and is no longer adequate to prevent reading ofinformation from the optical disk at the desired wavelengths emitted bythe lasers used for the players.

[0007] Organic dyes contemplated by U.S. Pat. No. 5,815,484 areconverted from a chemically reduced form or leuko state (non absorbingat the interrogating wavelength) to the desired colored state byoxidation via exposure to oxygen in ambient air to form a suitablyopaque state that absorbs light at the desired wavelengths. While thisprocess may be reversible, organic dyes generally can be “photobleached”using UV irradiation, such as readily available from sunlight, mercuryarc lamps, Xenon flash lamps, etc., and in certain cases loss of opacitycan be effected by simply exposing the reactive layer to elevatedtemperatures. The photo-stability (stability to bleaching processes) andheat stability of the dye is a fundamental problem with organic dyes notcontemplated by U.S. Pat. No. 5,815,484. Consequently, the specified andclaimed technology would require stabilizers and/or additionalprotective layers to obviate the obvious defeatability problems.

[0008] Another disadvantage with this technology is that it does notanticipate the roadmap for the migration from long to significantlyshorter wavelengths for semi-conductor lasers used, for example, by DVDplayers for reading of information from the optical disk. The currentlyused lasers irradiate with wavelengths at about 650 nm, while theroadmap devices currently being tested for product introduction as soonas 2002 will have interrogating wavelengths of only about 405 nm.Additionally, the technology does not contemplate the possibility of anoptical disc comprising the specified light absorbing reactive layer asbeing read by more that one type of player. For example, today DVDplayers commonly used on personal computers, can read both CD and DVDtype optical disk media. This requires the use of more than onewavelength for the interrogating laser employed to read information fromthe two types of optical disks, and additionally the intensity of thelasers and the signal to noise requirements of the photodetectors arenot the same. Accordingly, an optical disk that may be unplayable withone type of device may have acceptable play-back characteristics for asecond type of device, and thus the desired goal of limited play wouldnot necessarily be achieved. Moreover, the intensities of lasers differfor CD and DVD players made by different manufacturers, as do the signalto noise requirements of the optical pickups or detectors in theseplayers. Consequently, the degree of retained opacity necessary toprevent reading of information on a disk is not the same for one type ofmanufactured player versus another, and likely also varies as a functionof time of use of a particular player.

[0009] Other prior art, see for example U.S. Pat. No. 6,011,772 ofSpectraDisc Corp., describes a number of methods to limit optical discreadability. Corrosion of the reflective Al layer (or other metal usedto reflect light of the laser from information-encoding features so asto read the information on the disk) by the incorporation or delivery ofhumidity (water) to form an “electrolyte” at or near the surface of thereflective layer and thus catalyze corrosion is such a method. It ispreferred that selective corrosion of the Al layer occur so as to causesufficient loss in reflectivity of the Al layer to prevent opticalreading of the encoded information on the disk. This invention, howeverdoes not anticipate the current industrial practice incorporating aprotective barrier layer, typically SiOx which aggressively prevents thecorrosion of the metallic layer. The SiOx layer is necessary to preventpremature corrosion of the metal layer during manufacturing, especiallyin the case of Al reflective layers where the outermost 100 angstroms ofsputtered or vapor deposited layers is known to be completely oxidizedin microseconds even in substantially purified environments, a problemthat plagued the industry in the past. U.S. Pat. No. 6,011,772 specifiesthat the reflective layer of FIG. 16 is indeed protected by a barrierlayer to prevent such oxidation and physical damage, whereas U.S. Pat.No. 5,815,484 specifies in FIGS. 3, 5, 6, and 7 the use of a barrierlayer located adjacent to the reflective layer.

[0010] U.S. Pat. No. 6,011,772 further specifies the use of a barrierlayer that would be releasably coupled to the disk and that wouldprevent both machine-reading of the disk and activation of areading-inhibit agent (RIA). Consequently, the user of the optical diskwould be required to remove said barrier layer so as to allow forreading of the information on the disk. Removal of this barrier layer isspecified to activate a reading-inhibit agent that will subsequentlyalter the disk to inhibit reading of the disk after a certain time ofexposure of the disk to ambient environment that contains oxygen andmoisture and/or irradiation from the reading laser beam of the opticaldrive. The requirement for diffusion of oxygen and water vapor from theambient environment through a permeable layer, at a controlled rate, tothe metal layer is disadvantageous. The ambient environment is definedby where a particular player is used and thus does not take intoconsideration the considerable variability in humidity that generallyexists in different seasons and in different parts of a country or theworld in any season or even in the day versus the night. Accordingly,the limited play time of such a disk could be highly variable depending,for example, if the disk was even made for use in the same state, suchas for the case of Dallas versus Houston, Tex. where the relativehumidity can differ by at least 55%.

[0011] Additionally, U.S. Pat. No. 6,011,772 specifies that the readinhibiting agents (hereinafter “RIA”) can be activated bymachine-reading the disk such as by the optical radiation that isincident on the disk during machine-reading or by rotation of the diskduring machine-reading. This approach suffers from some of the samedeficiencies as described above for U.S. Pat. No. 5,815,484. In anotherembodiment of the barrier layer U.S. Pat. No. 6,011,772 specifies thatsaid layer is formed instead as a closed package that seals the entireoptical disk from contact with the ambient oxygen and moisture. Thisdoes not reduce the aforementioned disadvantage of requiring activationby both ambient oxygen and moisture.

[0012] In another embodiment U.S. Pat. No. 6,011,772 proposes to inhibitreading of information on the disk by incorporation of agents thatscatter the reading beam. The scattering mechanism disclosed employs anorganic solvent and a polymer layer. The polymer layer, when exposed toan organic solvent, depending on concentration and exposure time, willexperience a loss in transparency. In this case the read-inhibitingagent is stated to be the organic solvent working in concert with apolymer film. While this method may work to prevent readability, and isreadily effected using common solvents and polymer materials such aspolycarbonate, the practicality of dispensing a volatile organic solventin an electronic device is limited. Solvent flammability, toxicity, andvolatility, solvent caused corrosive effects on microelectroniccircuitry found in the player, and solvent caused deleterious structuralchanges to surfaces of the optical components and/or their mounts in theCD and/or DVD player would severely impact general usability andlifetime of the player. These and other effects resulting from use oforganic solvents for purposes of scattering the reading laser beam wouldsubstantially complicate the use and adoption of this embodiment of thespecified technology for the intended purpose of limiting the durationfor reading information from the said disk.

[0013] In another embodiment the inventor specifies the use of opticalradiation from a second optical source (i.e. high pressure arc lamp,fluorescent lamp, incandescent lamp, laser) to activate theread-inhibiting agent. The radiation source is coupled to theinterrogation beam such that the RIA is activated after the reading beamhas firstly read the data. While this method may provide a method toactivate the RIA, the coupling of such a secondary light source is notcurrently employed in standard optical disc play devices. Theincorporation of such an activation mechanism would limit the disc froma practicality standpoint unless the majority of DVD and/or CD playersincorporated the secondary light source. Moreover, activation of the RIAand the subsequent increase in absorbance of the wavelength used for thereading beam would require different amounts of absorbance for differentlevels of irradiance provided by reading beams in players from differentmanufacturers. U.S. Pat. No. 6,011,772 also describes a second sourcethat would be sufficiently strong so as to obviate need for a RIA, butin this case, for example, the light source could cause ablationcreating scattering centers that would limit access to information onthe disk immediately after the information is read. A simpler approachis further described as an alternative wherein the read/interrogationbeam could itself be used to activate the RIA. In this embodiment theRIA is contemplated to absorb some of the intensity of the interrogationread beam and then the activated RIA would attenuate the interrogatingbeam further and may inhibit proper reading of the data during the readlifetime of the disc.

SUMMARY OF THE INVENTION

[0014] This invention relates to a method of using materials that areapplied to a disk, card, media or the like, such as would be used forstoring information, such that upon subsequent exposure to an ambientcondition said applied material changes from a substantially transparentstate to one that is substantially more opaque as a consequence of thecreation of light scattering centers, color change, and/or reflectivitychange, thereby limiting the ability to read information from said disk,card, media or the like after the desired information has been read fromthe disk for a certain duration of time without the typicaldisadvantages of other methods such as susceptibility to photobleachingand/or lack of opacity to other wavelengths of light contemplated to beused to read the information.

[0015] The materials may be applied as a coating disposed as a protectedor non protected overlayer on a substrate that is in a confrontingrelationship with a reflecting metallic layer, said metallic layer beingencoded with the information data structures to be read or at leastdisposed as a layer on the structural features comprising suchinformation data structures, or the material may be interposed betweensaid metallic layer and the substrate, or superimposed over at least aportion of a plurality of readable data structures in the disk, card,media or the like, such as would be used for storing information, or thematerial may be applied in any other configuration including but notlimited to incorporation of the material into an adhesive bonding layersuch as used between the two sides of Digital Video Disks (DVD) or wouldbe contemplated for other optical disk or card technology comprising twoor more layers, or in other ways that would affect the ability tointerrogate the information data structures stored in an optical disk,card, media or the like such that when the material is activated itprevents reading of the disk, card, media or the like after an initialtime period during which the desired information data structures can beread from the disk, card, media or the like.

[0016] One embodiment of the present invention is an optical disk, cardor media for use in an optical read-out system that comprises a lightsource operative to produce an interrogating beam of light for readingdata structures. The optical disk, card or media comprises:

[0017] a. a plurality of data structures that are readable by theinterrogating beam of light; and

[0018] b. a composition on or in the optical disk, card or mediadisposed so that when the optical disk, card or media is used in theoptical readout system, the interrogating beam of light passes throughthe composition before or after contacting some or all of the datastructures. The composition comprises a polymeric matrix with anorganometallic complex dissolved therein or with metal, transitionmetal, metal oxide or transition metal oxide nanoparticles uniformlydispersed therein. The composition is substantially transparent to theinterrogating beam and/or is substantially colorless. Alternatively, thecomposition comprises: i) a solid polymeric matrix with an olefiniccompound dissolved or uniformly dispersed therein; and ii) a transitionmetal catalyst and a thiophenol or a catalytic amount of a thiylradical. The composition is substantially transparent to theinterrogating beam and/or is substantially colorless.

[0019] Another embodiment of the present invention is a method oflimiting access to data stored on the optical disk, card or mediadescribed above. The method comprises the step of exposing the opticaldisk, card or media to an ambient condition.

[0020] Another embodiment of the present invention is a method forcoating an internal or external surface of a device with a layer that issubstantially transparent to visible light. The layer is furthercharacterized in that it undergoes a reduction in said transparency whenexposed to an ambient condition. The method comprises the steps of:

[0021] a. dispensing onto the surface a film of a solution comprising atleast one monomer or at least one oligomer. The solution additionallycomprises an organometallic complex, metal, transition metal, metaloxide or transition metal oxide nanoparticles dissolved therein oruniformly dispersed therein. Alternatively, the solution comprises: i)at least one monomer or oligomer with an olefinic compound dissolved oruniformly dispersed therein; and ii) a transition metal catalyst and athiophenol or a catalytic amount of a thiyl radical; and

[0022] b. polymerizing the monomer(s) or oligomer(s) to form a polymer.

[0023] Another embodiment of the present invention is a method forcoating an internal or external surface of a device with a layer that issubstantially transparent to visible light. The layer undergoes areduction in said transparency when exposed to an ambient condition. Themethod comprises the steps of:

[0024] a. dispensing onto the surface a film of a solution comprising atleast one polymer. The solution additionally comprises an organometalliccomplex, metal, transition metal, metal oxide or transition metal oxidenanoparticles dissolved therein or uniformly dispersed therein.Alternatively, the solution comprises: i) at least polymer with anolefinic compound dissolved or uniformly dispersed therein; and ii) atransition metal catalyst and a thiophenol or a catalytic amount of athiyl radical; and

[0025] b. removing the solvent from the solution to form the coating.

DETAILED DESCRIPTION OF THE INVENTION

[0026] This invention describes the method of using a solution oforganometallic complexes in a polymeric material, referred to asmetal-polymer composites, that, for example, may comprise as thereading-inhibit agent (RIA) a colloidal dispersion of metal ortransition metal or metal-oxide or transition metal-oxide disperseduniformly as nano particulate in a polymeric matrix, so as to exhibit ahigh degree of transparency to desirable wavelengths of light for alimited time. The polymeric material and polymeric matrix can be, butare not limited to, a solid which can, for example, be characterized bya glass transition temperature that could be higher than 200° C. orlower to temperatures below room temperature, or a gel. Both rigid orhigh modulus and soft or low modulus solid polymers are contemplated.

[0027] Metal-polymer composites with a high degree of homogeneity can,by way of example, be prepared by mixing a polymer solution and theappropriate organometallic complex or precursor or by solution growthtechniques or direct implantation under influence of an electric fieldor by dissolution in solutions of functional polymers. Subsequenttreatment, such as chemical or thermal, or use of actinic radiation cantransform the organometallic complex into the corresponding metal ortransition metal or metal oxide or transition metal-oxide or some otherdesirable species. Under appropriate conditions, this transformedspecies will exist as a homogeneous dispersion of nanoparticles.“Nanoparticles” are defined to be particles having a dimension nogreater than about 50 nanometers in any one direction, preferablybetween about 5 to 30 nanometers in any one direction. Dry polymercoatings of such nanoparticle dispersions will be optically transparentsince the particulate size of the nanoparticles will be less than about{fraction (1/10)} the wavelength of visible light. Typically thesedispersions, and subsequent coatings maintain their homogeneity undercontrolled environmental conditions, such conditions being quite similarto those required for storage of proposed limited-play disks in theaforementioned prior art. Methods to control such environmentalconditions are consistent with those specified in the prior art.

[0028] This invention discloses, and in particular, describes the use ofcolloidal dispersions in a polymeric matrix as the RIA to limit thereadability of an optical medium. The colloidal metal, transition metal,metal oxide or the like, initially dispersed in a polymer solution,functional polymer solution, or in a monomer or oligomer containingmedium that is polymerizable by use of light and/or heat, exists in apolymer matrix layer that is substantially colorless and substantiallytransparent to an interrogating beam of optical irradiation for somedesirable limited amount of time, and where said desirable time isdefined by what is necessary and/or preferred for the intended use.Subsequently, the RIA can, for example, after exposure to ambientconditions become morphologically unstable forming aggregates thatexhibit substantially increased particulate size such that they act asscattering sites to visible wavelengths and/or change color orreflectivity or amount of transparency to said desirable wavelengths. Asused herein, “ambient conditions” means the conditions under which theRIA is typically used. Oxygen and moisture in the air, light used inoptical read-out systems and heat generated in optical read-out systemsare examples of conditions that are encompassed within the term “ambientcondition”, as it is used herein.

[0029] In one embodiment the colloidal dispersion is a metal ortransition metal, which when exposed to oxygen in the air or from someother source becomes oxidized to a metal oxide and, in turn changes thephysical nature of the dispersion which causes the development ofscattering centers throughout the polymer matrix.

xM⁰[O]→M_(x)O_(y)

[0030] where M includes but it not limited to elements such as Al, Si,Cr, Fe, Co, Ni, Cu, Zn, In, Sn, Ag, Au, Pt, Pd, Mo, and W. Thepreparation of the nano or colloidal dispersions of metals is known inthe art and is described for example, in T. W. Smith and D. Wychick J.Phys. Chem. 1980, 84, 1621-1629, H. H. Huang etal. Langmuir 1996, 12,909-912 and H. Hirai, H. Wakabayashi and M. Komiyama, Bull.Chem. Soc.Jpn., 1986 59, 367-372, the entire teachings of which are incorporatedherein by reference.

[0031] In another embodiment a colloidal dispersion of a noble metalsuch as Au, Pt or Pd can be prepared as the RIA. Dispersions of thistype are stabilized by specific interactions between the metal andligands in the dispersion. These dispersions are stable when protectedfrom light or heat or air and in particular O₂. Exposure to variousambient conditions destabilizes the ligand-metal interaction causing thenoble metal to phase separate or agglomerate, thereby forming aggregatesthat scatter visible light or in extreme cases the film can becomesubstantially reflective to light. In some cases the metal may undergo achemical reaction forming a new species, such as a metal oxide, thatwill change the color of the polymer layer and/or cause scattering byprecipitation or by a change in the refractive index of the metal whenit transforms to the metal oxide.

[0032] Alternately, the RIA could be a material that when dispersed ordissolved in a polymeric matrix forms a layer with high transparency todesirable wavelengths of light, and upon subsequent exposure to ambientconditions the material undergoes a phase change, chemical reaction orisomenzation of unsaturated chemical bonds in its chemical structure tosubstantially reduce the transparency of the film to said desirablewavelengths. The chemical reaction could, by way of example, becatalyzed carbon-carbon double bond cleavage due to olefin oxidation,such as can be promoted by a transition metal catalyst and a thiophenol,or catalytic amounts of a thiyl radical (see X. Baucherel, J. Uziel andS. Juge in J. Org. Chem. 2001, 66, 4504-4510, the entire teachings ofwhich are incorporated herein by reference). Suitable olefins includearyl olefins, aliphatic olefins, functionalized olefins (e.g.,functionalized with esters, ketones, nitrites, carboxylic acids and thelike); suitable transition metal catalysts include MnCl, V(acac)₃, VCl₃,Vanadium oxo bis(1-phenyl-1,3-dibutanedionate and the like); andsuitable thiophenols include unsubstituted thiophenol and thiophenolssubstituted with halogens, alkyl groups and the like. Other suitableolefins, transition metal catalysts and thiophenols are disclosed inBaucherel et al.

[0033] The RIA can be incorporated as a coating on all or part of asurface (internal or external surface) of device for which a change intransparency and/or coloration is desirable upon exposure to an ambientcondition. The RIA can also be incorporated as a complete or partialcoating on a part from which such a device is assembled. Examples ofsuch devices include an optical disc, card, media (such as holographicrecording medium) and the like. The RIA can be applied between theinformation carrying layer comprising data structures or the reflectivelayer encoded with said information data structures, said reflectivelayer may be disposed as a layer on the features comprising suchinformation data structures, and the topmost or bottom surface of thedisk, card, media or the like or the RIA may be in the topmost or bottomlayer of the disk, card, media or the like, or it may be incorporated asan adhesive bonding layer such as used between the two sides of DVDoptical disks, or may be contemplated for use in multilayer opticaldisks, cards, media or the like, comprising two or more informationcarrying layers comprising data structures, or in other ways that wouldeffect the ability to interrogate and read the information datastructures stored in or on an optical disc, card, media or the like. TheRIA can be incorporated, for example, as a coating on all or part of aholographic recording medium so that the imaging beam(s) pass throughthe RIA before or after contacting some or all of the data structures.Holographic recording mediums are disclosed in U.S. Pat. No. 6,212,148,WO 01/90817 and WO 97/13183, the entire teachings of which areincorporated herein by reference. A “data structure” is a structure inan optical disk, card or media that stores information. In a CD or DVD,the data structures are a sequence of pits and lands; in a holographicrecording medium, the data structures are regions or holographicrecording; and in a phase change medium such as a writable CD or DVD,the data structures are related to regions of phase change.

[0034] More specifically, organometallic complexes that are used for theRIA of the solid solution can be prepared by dissolving metal ortransition-metal carbonyl compounds in polymers or in materialscomprising one or more polymerizable monomer(s) and/or oligomer(s).Solutions formed from the metal or transition-metal compounds andpolymers can, for example, be cast into solid films on a surface such asthe substrate, the metallized layer, a barrier layer, or other layerscontemplated for optical disks, cards, media or the like, whereassolutions comprising polymerizable monomers and/or oligomers can bedispensed onto any of the aforementioned surfaces or other layerscontemplated for optical disks, cards, media or the like or into a gapbetween two such surfaces, and the monomers and/or oligomers can besubsequently polymerized to form a solid film by use of actinicradiation or heat or combinations thereof. Decomposition of the metal ortransition-metal compounds to form uniform metal oxide dispersionscauses significant changes to the particle size exhibited by thesematerials such that the solid solution changes from a substantiallytransparent non-absorbing state, for desirable wavelengths of light, toa state that scatters light effectively over a broad range of desirablevisible wavelengths extending from violet or short blue to red or evento near IR. The polymer or subsequently polymerized monomers oroligomers can additionally serve as a catalyst, via nonbonded dispersiveVan der Waals interactions and electrostatic type interactions, such ascharge-charge, charge-dipole or dipole-dipole, for the desireddecomposition of the metal or transition-metal carbonyl compounds (seefor example T. W. Smith and D. Wychick, J. Phys. Chem. 84, 1621 (1980)).Fe(CO)₅ is one such example of an organometallic complex that, by way ofexample, as a liquid can be dissolved in polymers and thusly prepared asa homogeneous solid solution in polymer films

[0035] Films comprising, for example, Fe(CO)₅ can exhibit acutesensitivity to UV radiation causing rapid formation of the reactiveintermediate Fe(CO)₄ which reacts with excess Fe(CO)₅ to form Fe₂(CO)₉.The latter compound is substantially more susceptible to oxidation andsubsequent decomposition to iron oxide, Fe₂O₃, can occur in relativelyshort time periods as a consequence of exposure to ambient conditionscomprising air. Films that are adequately shielded from light and/or airor are adequately protected by a shielding layer, however, can be keptfor long periods in the presence of air without exhibiting significantdecomposition.

[0036] Another example of such an organometallic complex that, by way ofexample, can be used to form solid solutions in a broad spectrum ofpolymers is Co₂(CO)₈ (see P. H. Hess and H. Parker, Jr. Appl. Polym.Sci., 10, 1915 (1966)), and the resultant oxidation products are CoO andCo₂O₃. One advantage of using organometallic complex materials as theRIA is that they can be readily prepared in solutions using standardorganic solvents or in solutions of polymers or functional polymers orusing polymerizable monomers and/or oligomers, and these solutionsexhibit substantially enhanced stability to decomposition and subsequentoxidation as compared to solid solutions (see for example R. Tannenbaum,C. L. Flenniken and E. P. Goldberg, XI International Conference onOganometallic Chemistry, 1983, p.77) that would be used as film typelayers in or on an optical disk, card, or the like. This is beneficialfrom the standpoint of preparing materials for coatings in a way that isconsistent with manufacturing processes. Moreover, activation energiesfor decomposition of, for example, the Fe(CO)₅ complex can exceed 35kcal/mole in a solid solution of polymethylmethacrylate and 45 kcal/molein polycarbonate (see R. Tannenbaum, E. P. Goldberg, and C. L.Flenniken, “Decomposition of Iron Carbonyls in Solid Polymer Matrices:Preparation of Novel Metal-Polymer Composites” in Metal-ContainingPolymeric Systems, eds. J. E. Sheats, C. E. Carraher, Jr., and C. U.Pittman, Jr., Plenum Press, New York, 1985, pp. 320-327), values thatare consistent with many of years of storage of a disk comprising saidcomplex prior to intended use. Activation of the Fe(CO)₅ or Co₂(CO)₈complex can be accomplished by exposure to UV radiation (see for exampleG. O. Schenck, E. Koerner van Gustorf and Mon-Jon Tun, TetrahedronLetters, 1059 (1962)). Protection against subsequent oxidation in thepresence of air can be provided, independently or in combination, by useof a barrier layer or use of inert gas in packaging of the optical disk,card, or the like or use of oxygen scavengers commonly found inpackaging of foods, or other such methods independently or incombination so as to prevent or slow down diffusion of oxygen to thelayer containing the RIA material. Exposure to UV radiation for purposesof activating the RIA material for subsequent oxidation can be readilyimplemented as part of the manufacturing process of the limited playoptical disks, cards, or the like, such as would be used for an inlineor continuous-batch photolytic process that initiates polymerizationreactions in solutions comprising the RIA and monomers and/or oligomers.

[0037] Polymers that are suitable for use in the disclosed compositionsand methods are substantially optically transparent and substantiallycolorless. “Substantially optically transparent” and “substantiallycolorless” means that when the polymer is incorporated into or onto anoptical disk, card or media, the polymer does not interfere with theability of the interrogating beam of light used in the optical read-outsystem being used to read the optical disk, card or media. Preferredpolymers are thermoplastic polymers and/or are formed fromphotopolymerizable or thermopolmerizable monomer(s) and/or oligomer(s)comprising, but not limited to, ethylenically unsaturated groups,epoxide groups or combinations thereof Examples of suitable polymersinclude, but are not limited to polystyrenes, polyacrylates,polyacrylonitriles, polyesters, polycarbonates, polysulfones,polyalkylene oxides, polypyrrolidones, polyamides, polyurethanes,polythiazoles, poysiloxanes, polyphthalates, or copolymers thereof.Another example includes polymers formed from hydrosilylation reactionswith, for example, vinylfunctionalized groupings and hydrofunctionalizedsiloxanes. Typically, polymers suitable for use in the disclosedinvention have a threshold molecular weight greater than 1000 amu.

[0038] Advantageously, the method contemplated in this invention doesnot require any significant or difficult changes to the existingmanufacturing methodology used, for example, to prepare optical discsfor CD and/or DVD players. Additionally, the method does not requirespecial modification to the existing read device technology. Moreover,this methodology does not require the incorporation of hazardousvolatile components to activate the RIA, nor does it incorporate orcreate chemical species that would interact unfavorably with componentsof the read device (i.e. optical head) or of the optical drive itself.Additionally, and perhaps most importantly, this invention provides amethod to limit the play time of an optical disc or card in a opticaldrive, such as DVD or CD player, in a manner which can not be defeatedby photo-bleaching of the RIA, or by changing the wavelength of theinterrogating beam.

EXAMPLE

[0039] (1) A typical formulation comprising the RIA contemplated by thisinvention is a formulation that preferably can be coated or delivered toa surface or between surfaces by normal means, such as spin coating, dipcoating or the like, and is deposited on recording media as a coating oras an interstitial adhesive layer in a multilayer disc, card, or thelike. The delivered formulation preferably can be cured or crosslinkedby normal techniques, such as use of actinic radiation or heat, oralternatively it may be cast from a solution into a polymer film withoutrequiring a cure. The cured, crosslinked or cast film or interstitiallayer is positioned intermediate between the stored information dataand/or file directory structures and the detector used to read saidstored information data and/or file directory structures. In such anarrangement the interrogating beam used to read the media must traversesaid coating or layer at least once. The formulation, by way of example,comprises an organometallic complex, a polymerizable component orcomponents, optionally a binder polymer or oligomer, optionally acrosslinkable functional polymer or oligomer, and polymerizationinitiation system. Alternatively, the formulation comprises anorganometallic complex and a polymer or functional polymer or copolymer,or combinations thereof. The organometallic complex can be any number ofmaterials that degrade in the presence of oxygen such ascyclopentadienyl complexes of chromium, nickel, cobalt, titanium,tungsten or platinum or ruthenium or others described in the abovespecification of the invention such as an Fe(CO)₅ complex or Co₂(CO)₈complex. Another desirable feature of these organometallic complexeswould be the apparent auto-catalytic behavior these materials exhibitupon decomposition. This would allow for good control of the kinetics ofdecomposition and offer a superior product over other candidates. (2) Atypical formulation comprising the RIA contemplated by this invention isa formulation that preferably can be coated or delivered to a surface orbetween surfaces by normal means, such as spin coating, dip coating orthe like, and is deposited on recording media as a coating or as aninterstitial adhesive layer in a multilayer disc, card, or the like. Thedelivered formulation preferably can be cured or crosslinked by normaltechniques, such as use of actinic radiation or heat, or alternativelyit may be cast from a solution forming a polymer film without requiringa cure. The cured, crosslinked or cast film or interstitial layer ispositioned intermediate between the stored information data and/or filedirectory structures and the detector used to read said storedinformation data and/or file directory structures. In such anarrangement the interrogating beam used to read the media must traversesaid coating or layer at least once. The formulation, by way of example,comprises a colloidal suspension of a metal such as platinum, palladium,gold, or silver, a polymerizable component or components, optionally abinder polymer or oligomer, optionally a crosslinkable functionalpolymer or oligomer, and polymerization initiation system, such that theligand-colloidal particle interaction or other electrostatic ordispersive interaction stabilizing the colloid can be destabilized inthe presence of oxygen leading to agglomeration and/or phase separationthereby forming particulates or aggregates that scatter light. In suchan example a surfactant or surfactant-like grouping is, by way ofexample, independently, a monovalent substituted or unsubstitutedthio-alkyl, thio-cycloalkyl, thio-arylalkyl, sulfide, or disulfideligand that is used to stabilize a colloidal suspension of a noble metalsuch as gold. It is well understood that specific interactions betweenthe alkanethiol, sulfide, and disulfide ligand and the nanoparticle leadto stable colloidal suspensions. It has also been observed that theinteraction between the alkanethiol, sulfide or disulfide ligand and thenanoparticle are susceptible to air oxidation, destabilizing theligand-metal interaction leading to agglomeration or aggregation of thenano-particles. Such aggregation substantially increases the size of theparticles and consequently visible light will be scattered at locationsof these particles in the suspension. Similar behaviors are observed foralkyl carboxylic acid stabilized colloidal suspensions of, for example,Fe, Al, Cu and Co.

EXEMPLIFICATION Example 1

[0040] A transparent coating of a precursor to a read inhibiting agentwas prepared in the following manner. In a glove box or other suchinert, oxygen free environment, a vial was charged with 2.0 grams of anoptical adhesive, OP21 from Dymax Corporation and 0.4 grams of Ironpentacarbonyl. Following mechanical stirring a homogenous formulationwas obtained. Two cells for testing the RIA were prepared by sandwichingthe formulation between two glass slides, a base and a cover slip. Theformulation was left to cure in ambient light, ˜30 min. Next, one of thetwo cells was removed from the glove box and the cells cover slip wascarefully removed. The pale yellow film was left exposed to ambientconditions. After 5 hours the film had become dark brown in color. Thecontrol sample in the glove box remained transparent pale yellow.

Example 2

[0041] A transparent coating of a precursor to a read inhibiting agentwas prepared in the following manner. In a glove box or other suchinert, oxygen free environment, a vial was charged with 10 grams of a 50wt % solution of Polystyrene (Aldrich product 33,165-1) in toluenepreviously degassed with N₂. Next a solution of Ni(COD)2 in toluene, 250mg of Ni(COD)2 in 5 mL of toluene was added to the polymer solution.After thorough mixing the yellow orange solution was applied, via spincoating, to glass substrate. After drying the pale orange film wasexposed to ambient conditions. After 1 hour the film developed hazewhich became quite pronounced after ˜5 hours of exposure to ambientconditions.

Example 3

[0042] A transparent coating of a precursor to a read inhibiting agentwas prepared in the following manner. In a glove box or other suchinert, oxygen free environment, a vial was charged with 3.0 grams of DowCorning 93-500 Base, 0.30 grams of Dow Corning 93-500 curing agent and3.3 mL of Toluene. To the polymer solution was added 0.150 grams ofNi(COD)₂ dissolved in 3 mL of toluene. After thorough mixing the yelloworange solution was applied, via dip coating, to glass substrate. Afterdrying the pale orange film was exposed to ambient conditions. After 1hour the film developed haze which became quite pronounced after ˜3hours of exposure to ambient conditions.

[0043] The resulting reduction in transparency was evaluated usingillumination from a frequency doubled diode pumpled solid state laseremitting at 532 nm. The spot dimensions corresponding to the area ofillumination was a square of 3 mm by 3 mm. The transmitted intensitydeclined by a factor of between 4 and 17.5 depending upon the thicknessof the coated film. The decline in transparency occurred resulted fromthe light being diffused into a larger area as a consequence of the hazethat was formed in the film.

[0044] While this invention has been particularly shown and describedwith references to preferred embodiments thereof, it will be understoodby those skilled in the art that various changes in form and details maybe made therein without departing from the scope of the inventionencompassed by the appended claims.

What is claimed is:
 1. An optical disk, card or media for use in anoptical read-out system that comprises a light source operative toproduce an interrogating beam of light for reading data structures,wherein the optical disk, card or media comprises: a. a plurality ofdata structures that are readable by the interrogating beam of light; b.a composition on or in the optical disk, card or media disposed so thatwhen the optical disk, card or media is used in the optical read-outsystem, the interrogating beam of light passes through the compositionbefore or after contacting some or all of the data structures, whereinthe composition comprises a polymeric matrix with an organometalliccomplex dissolved therein or with metal, transition metal, metal oxideor transition metal oxide nanoparticles uniformly dispersed therein andwherein the composition is substantially transparent to theinterrogating beam and/or is substantially colorless.
 2. The opticaldisk or card of claim 1 further comprising: a. a metallic layer; and b.a substrate disposed in a confronting relationship with the metalliclayer.
 3. The optical disk or card of claim 2 wherein the composition isa film superimposed over at least some of the data structures.
 4. Theoptical disk or card of claim 2 wherein the composition is interposedbetween the metallic layer and the substrate.
 5. The optical disk orcard of claim 2 wherein the organometallic complex or nanoparticlesreact when exposed to an ambient condition to form a product whichreduces the transparency of the composition to the interrogating beamand/or increases the coloration of the composition.
 6. The optical diskor card of claim 2 wherein the organometallic complex or nanoparticlesreact when exposed to oxygen, moisture, light and/or heat to form aproduct which reduces the transparency of the composition to theinterrogating beam and/or increases the coloration of the composition.7. The optical disk or card claim 6 wherein the composition is a solidsolution of an organometallic complex dissolved in a polymeric matrix.8. The optical disk or card of claim 7 wherein the organometalliccomplex is a cyclopentadienyl or CO complex of iron, chromium, nickel,cobalt, titanium, tungsten, platinum or ruthenium.
 9. The optical diskor card of claim 8 wherein the organometallic complexes is Fe(CO)₅complex, Co₂(CO)₈ complex or nickel cyclooctoadiene complex.
 10. Theoptical disk or card of claim 6 wherein the composition is a solidpolymeric matrix with metal, transition metal, metal oxide or transitionmetal oxide nanoparticles uniformly dispersed therein.
 11. The opticaldisk or card of claim 10 wherein the metal or transition metalnanoparticles oxidize when exposed to air.
 12. The optical disk or cardof claim 11 wherein metal or transition metal is Al, Si, Cr, Fe, Co, Ni,Cu, Zn, In, Sn, Ag, Au, Pt, Pd, Mo or W.
 13. The optical disk or card ofclaim 10 further comprising a ligand which stabilizes the metal ortransition metal nanoparticles.
 14. The optical disk or card of claim 13wherein the metal or transition metal is Au, Ag, Pt or Pd and the ligandis a monovalent substituted or unsubstituted thio-alkyl,thio-cycloalkyl, thio-arylalkyl, sulfide or disulfide ligand.
 15. Theoptical disk or card of claim 13 wherein the metal or transition metalis Fe, Al, Cu or Co and the ligand is an alkyl carboxylic acid.
 16. Theoptical disk or card of claim 6 wherein the polymeric matrix is athermoplastic polymer.
 17. The optical disk or card of claim 6 whereinthe polymeric matrix is formed from a photopolymerizable orthermopolmerizable monomer and/or oligomer comprising ethylenicallyunsaturated groups, epoxide groups or combinations thereof.
 18. Anoptical disk, card or media for use in an optical read-out system thatcomprises a light source operative to produce an interrogating beam oflight for reading data structures, comprising: a. a plurality of datastructures that are readable by the interrogating beam of light; and b.a composition on or in the optical disk disposed so that when theoptical disk, card or media is used in the optical read-out system, theinterrogating beam of light passes through the composition before orafter contacting some or all the of the data structures, wherein thecomposition comprises: i) a solid polymeric matrix with an olefiniccompound dissolved or uniformly dispersed therein; and ii) a transitionmetal catalyst and a thiophenol or a catalytic amount of a thiyl radicaland wherein the composition is substantially transparent to theinterrogating beam and/or is substantially colorless.
 19. The opticaldisk or card of claim 18 further comprising: a. a metallic layer; and b.a substrate disposed in a confronting relationship with the metalliclayer.
 20. A method for coating an internal or external surface of adevice with a layer that is substantially transparent to visible lightwherein the layer undergoes a reduction in said transparency whenexposed to an ambient condition, said method comprising the steps of: a.dispensing onto the surface a film of a solution comprising at least onemonomer or at least one oligomer, wherein the solution additionallycomprised an organometallic complex, metal, transition metal, metaloxide or transition metal oxide nanoparticles dissolved therein oruniformly dispersed therein; and b. polymerizing the monomer(s) oroligomer(s) to form a polymer.
 21. The method of claim 20 wherein thedevice is an optical disk or card or a part used in the manufacture ofan optical disk or card.
 22. The method of claim 21 wherein the deviceis a substrate, metallized layer, information carrying layer or barrierlayer used in the manufacture of an optical disk or card.
 23. The methodof claim 21 wherein the organometallic complex or nanoparticles reactwhen exposed to an ambient condition to form a product which reduces thetransparency of the layer or increases the coloration of the layer. 24.The method of claim 21 wherein the organometallic complex ornanoparticles react when exposed to an ambient condition to form lightscattering centers.
 25. The method of claim 22 wherein theorganometallic complex or nanoparticles react when exposed to oxygen,moisture, light and/or heat to form a product which reduces thetransparency of the polymerized monomer or increases the coloration ofthe layer.
 26. The method claim 25 wherein the monomer solutioncomprises an organometallic complex dissolved therein.
 27. The method ofclaim 26 wherein the organometallic complex is a cyclopentadienyl or COcomplex of iron, chromium, nickel, cobalt, titanium, tungsten, platinumor ruthenium.
 28. The method of claim 27 wherein the organometalliccomplex is Fe(CO)₅ complex, Co₂(CO)₈ complex or nickel cyclooctadiene.29. The method of claim 25 wherein the monomer solution comprises metal,transition metal, metal oxide or transition metal oxide nanoparticlesuniformly dispersed or dissolved therein.
 30. The method of claim 29wherein the metal or transition metal nanoparticles oxidize when exposedto air.
 31. The method of claim 30 wherein metal or transition metal isAl, Si, Cr, Fe, Co, Ni, Cu, Zn, In, Sn, Ag, Au, Pt, Pd, Mo or W.
 32. Themethod of claim 29 wherein the monomer solution further comprises aligand which stabilizes the metal or transition metal nanoparticles. 33.The method of claim 32 wherein the metal or transition metal is Au, Ag,Pt or Pd and the ligand is a monovalent substituted or unsubstitutedthio-alkyl, thio-cycloalkyl, thio-arylalkyl, sulfide or disulfideligand.
 34. The method of claim 32 wherein the metal or transition metalis Fe, Al, Cu or Co and the ligand is an alkyl carboxylic acid.
 35. Themethod of claim 25 wherein the monomer solution comprise one or moremonomers or oligoner(s) which form thermoplastic a polymer whenpolymerized.
 36. The method of claim 25 wherein the monomer or oligomeris olefinic or epoxy monomer or oligomer that is photopolymerizable orthermopolymermizable.
 37. A method for coating an internal or externalsurface of a device with a layer that is substantially transparent tovisible light wherein the layer undergoes a reduction in saidtransparency when exposed to an ambient condition, said methodcomprising the steps of: a. dispensing onto the surface a film of asolution comprising: i) least one monomer or oligomer with an olefiniccompound dissolved or uniformly dispersed therein; and ii) a transitionmetal catalyst and a thiophenol or a catalytic amount of a thiylradical; and b. polymerizing the monomer.
 38. A method for coating aninternal or external surface of a device with a layer that issubstantially transparent to visible light wherein the layer undergoes areduction in said transparency when exposed to an ambient condition,said method comprising the steps of: a. dispensing onto the surface afilm of a solution of at least one polymer, wherein the solutionadditionally comprises an organometallic complex, metal, transitionmetal, metal oxide or transition metal oxide nanoparticles dissolvedtherein or uniformly dispersed therein; and b. removing the solvent fromthe solution to form the coating.
 39. The method of claim 38 wherein thedevice is an optical disk or card or a part used in the manufacture ofan optical disk or card.
 40. The method of claim 39 wherein the deviceis a substrate, metallized layer, information carrying layer or barrierlayer used in the manufacture of an optical disk or card.
 41. The methodof claim 39 wherein the organometallic complex or nanoparticles reactwhen exposed to an ambient condition to form a product which reduces thetransparency of the layer or increases the coloration of the layer. 42.The method of claim 39 wherein the organometallic complex ornanoparticles react when exposed to an ambient condition to form lightscattering centers.
 43. The method of claim 40 wherein theorganometallic complex or nanoparticles react when exposed to oxygen,moisture, light and/or heat to form a product which reduces thetransparency of the polymerized monomer or increases the coloration ofthe layer.
 44. The method claim 43 wherein the monomer solutioncomprises an organometallic complex dissolved therein.
 45. The method ofclaim 44 wherein the organometallic complex is a cyclopentadienyl or COcomplex of iron, chromium, nickel, cobalt, titanium, tungsten, platinumor ruthenium.
 46. The method of claim 45 wherein the organometalliccomplex is Fe(CO)₅ complex, Co₂(CO)₈ complex or nickel cyclooctadiene.47. The method of claim 43 wherein the monomer solution comprises metal,transition metal, metal oxide or transition metal oxide nanoparticlesuniformly dispersed or dissolved therein.
 48. The method of claim 47wherein the metal or transition metal nanoparticles oxidize when exposedto air.
 49. The method of claim 48 wherein metal or transition metal isAl, Si, Cr, Fe, Co, Ni, Cu, Zn, In, Sn, Ag, Au, Pt, Pd, Mo or W.
 50. Themethod of claim 47 wherein the monomer solution further comprises aligand which stabilizes the metal or transition metal nanoparticles. 51.The method of claim 50 wherein the metal or transition metal is Au, Ag,Pt or Pd and the ligand is a monovalent substituted or unsubstitutedthio-alkyl, thio-cycloalkyl, thio-arylalkyl, sulfide or disulfideligand.
 52. The method of claim 50 wherein the metal or transition metalis Fe, Al, Cu or Co and the ligand is an alkyl carboxylic acid.
 53. Themethod of claim 43 wherein the monomer solution comprise one or moremonomers or oligoner(s) which form thermoplastic a polymer whenpolymerized.
 54. The method of claim 43 wherein the monomer or oligomeris olefinic or epoxy monomer or oligomer that is photopolymerizable orthermopolymermizable.
 55. A method for coating an internal or externalsurface of a device with a layer that is substantially transparent tovisible light wherein the layer undergoes a reduction in saidtransparency when exposed to an ambient condition, said methodcomprising the steps of: c. dispensing onto the surface a film of asolution comprising: i) at least one polymer, with an olefinic compounddissolved or uniformly dispersed therein; and ii) a transition metalcatalyst and a thiophenol or a catalytic amount of a thiyl radical; andd. removing the solvent from the solution to form the coating.
 56. Amethod of limiting access to data stored on an optical disk, card,media, said optical disk, card or media being used in an opticalread-out system that comprises a light source operative to produce aninterrogating beam of light for reading data structures, said methodcomprising the step of exposing the optical disk, card or media to anambient condition, wherein the optical disk, card or media comprises: a.a plurality of data structures that are readable by the interrogatingbeam of light; b. a composition on or in the optical disk, card or mediadisposed so that when the optical disk, card or media is used in theoptical read-out system, the interrogating beam of light passes throughthe composition before or after contacting some or all of the datastructures, wherein the composition comprises a polymeric matrix with anorganometallic complex dissolved therein or with metal, transitionmetal, metal oxide or transition metal oxide nanoparticles uniformlydispersed therein and wherein the composition is substantiallytransparent to the interrogating beam and/or is substantially colorless.57. The method of claim 56 wherein the ambient condition is exposure tothe interrogating beam of light.
 58. A method of limiting access to datastored on an optical disk, card, said optical disk, card or media beingused in an optical read-out system that comprises a light sourceoperative to produce an interrogating beam of light for reading datastructures, said method comprising the step of exposing the opticaldisk, card or media to an ambient condition, wherein the optical disk,card or media comprises: a. a plurality of data structures that arereadable by the interrogating beam of light; and b. a composition on orin the optical disk disposed so that when the optical disk, card ormedia is used in the optical read-out system, the interrogating beam oflight passes through the composition before or after contacting some orall the of the data structures, wherein the composition comprises: i) asolid polymeric matrix with an olefinic compound dissolved or uniformlydispersed therein; and ii) a transition metal catalyst and a thiophenolor a catalytic amount of a thiyl radical and wherein the composition issubstantially transparent to the interrogating beam and/or issubstantially colorless.
 59. The method of claim 58 wherein the ambientcondition is exposure to the interrogating beam of light.